A series of novel Eu3+-activated Ba2Gd2/3TeO6 (BGT) phosphors were successfully synthesised via a high temperature solid state reaction method. The crystal structure analysis showed that Eu3+-doped Ba2Gd2/3TeO6 double perovskite phosphors possess monoclinic symmetry with space group P21/n. The as-prepared phosphors can be efficiently excited by far-ultraviolet light to generate reddish orange luminescence of around 593 nm corresponding to the 5D0 → 7F1 transitions of Eu3+ ions. Gd3+ acts as a sensitizer for luminescence enhancement. The highest luminescence intensity corresponded to x = 0.11 Eu3+ concentration, and the critical distance was calculated to be 9.61 Å, indicating that multipolar interaction is behind the concentration quenching mechanism. Besides, the optimum concentration Eu3+-activated Ba2Gd2/3TeO6 phosphor exhibited color co-ordinates of (0.63, 0.36), a high color purity of 94.21% and a quantum efficiency of 18%. JO intensity parameters reveal the slight distortion of the crystal field around the activator ion. Notably, the maximum relative sensitivities of the BGT:0.11Eu3+ phosphor were found to be 0.19% K-1 within the temperature range of 300-500 K and 2.07% K-1 within 80-300 K, and it can potentially be used as a promising thermometer in high and low temperature regions, respectively. The luminescent labels based on fluorescent ink and PL chalk demonstrate the potential application of synthesized phosphors in anti-counterfeiting and security labeling.